Process of making saturated acids, by simultaneous dissociation and hydrogenation



- stance, Ubbelohde Handbuch der Chemie' und the fat which is supplied with the catalyst. Also 110' Patented Mar. 27, 1934 g t I l UNlTED STATES PATENT OFFICE PROCESS OF MAKING SATURATED ACIDS,- BY SIMULTANEOUS DISSOCIATION AND HYDROGENATION Hans Kaufmann, Jena, Germany No Drawing. Application November 13, 1929, Sgrial No. 406,975. In Germany December 27, 1 28 6 Claims. (01. 87-12) This invention relates to a process of making 'I'echnologie der Oele und Fette, Liepzig'1928, saturated acids, preferably from fats, and more volume IV,'page 309, third from last'line). It particularly to a process of increasing the per has also been so far the opinion of experts that cent in mixtures of fatty acids and consists essenlosses would eventually take place due to the fortially in combining the catalytic hydrogenation mation of compounds with the catalyst. There so and the hydrolytic splitting into a single operais further the general opinion among experts that tion. glycerine is a catalyst poison. Therefore either For many technical purposes saturated fatty failure of the catalyst during the course of the acids are of greater-importance than non-satprocess of hardening, the degree of failure of the 10 urated fatty acids. Thus, for instance, in the catalyst increasing with the formation of glycer- 5 candle-industry and partly also in the soap-inine, or also a loss of said catalyst due to formadustry there are preferably used the solid sattion of a compound with the fatty acids was to urated acids which are obtained by splitting the be expected according to the general opinion. As fat. If it is desired to make use of natural fats a matter of surprise I have found that neither which mainly contain liquid non-saturated acids said failure of the catalyst nor said formation of 70 (oils), said natural fats are first hydrogenized and a compound takes place. In particular I have'asthereupon the hardened fats are split off or certained that nickel will not be dissolved by worked into soaps. fatty acids in an atmosphere of hydrogen, if

An essential simplification of the process now water-steam of high temperature is present. In

is attained according to my invention by carrycase soaps of nickel should be formed, they may 15 ing out the hydrogenation as well as the process be split hydrolytically and the hydroxide will at of splitting in a single step of operation. In the once be reduced to metal. Nor does a poisoning German Patent 126,446 and the further addiof the catalyst take place and on the contrary I tional. German Patent 132,223 there is described have found that the catalyst may be used without 5 a process of splitting fatty substances and at reactivation a great many times, if the fats are so I the same time transforming liquid fatty acids previously carefully purified. into solid fatty acids by treating the fats with When carrying out the process according to sulphuric acid and exposing the intermediary my invention. all ordinary methods of splitting substances, that is the sulphuric acid ester of the and likewise all well-known methods of catalytic fatty acids simultaneously to pressure, heat and hydrogenation for instance with catalysts of 85 electric current. It may be assumed that the nickel may be used. The process maybe carried produced solid fatty acids represent isomers of through after the reaction mass had been supthe non-saturated initial fatty acids in accordplied with the catalyst and by passing'hydrogen ance with known methods for producing at room (or a gas containing hydrogen) through said re- 7 e perature solid isomers of the non-saturated ,action mass. The degree of splitting is dependent 90 acids. Also the short statementsregarding-the upon the quantity of the splitting agent, upon apparatus to be used would lead to the conclusion the duration of the process as well as upon the that the aforementioned methods appear to retemperature. Hardening is regulated, besides late to the formation. of solid acids from liquid temperature and pressure of the hydrogen, by

40 acids. Apparently no hydrogenation takesplace the quantity and quality of the catalyst. Con- ,95 in this case. sidering these facts there may be made mixtures It hasfurther been found that the simultane of' saturated and non-saturated acids of a deous splitting as well as the addition of, hydrogen sired composition, from oils, in case a complete y be Carried 01111 in a technically uitabl ma hydrogenation is not desired. The presence of or. f ca y i hydrogenation s empl yed. D hydrogen-in addition, is connected with the ad- 100 to the presence of considerable quantities of wavantage that reactions due to decompositionter and the formation of glycerine, conditions will hi h 511 u; in darkening t i proalise Which-like hydrogenation in a w -p a e (mood-may be effectively prevented, even at high System in gellelalal'e q e ffe nt f om the pressures and temperatures. Furthermore, the

conditions-which prev il Wh nusing the ordiheat which is developed by-exothermic reaction 1 y process of hardening ACCOrdiIlg to the during hydrogenation may be, made available for p e Opinion f experts the presence of. relathe process of splitting. When using water-steam tively large quantities of water will have an un- I in condition of flow, said steam mixed with hyav a effect up t a d i e. for indrogen may be continuously circulated through the fat mixed with the catalyst may be atomized in an atmosphere of hydrogen and water-steam. The process of working-up the reaction mass may be carried out in that said reaction mass is allowed to settle in several layers by cooling under pressure or by passing said reaction mass in still Examples 1. 10 parts of oil acid methyl ester and 5 parts of water are caused to interact in a stirring digestor with 0.2 part of magnesium oxide and 2 parts of a nickel infusorial silica catalyst (Nicontents 20%) and the air is driven out of the apparatus by hydrogen. The mixture is heavily agitated and now warmed to a temperature of about 200, the consumed hydrogen being replaced from time to time. Samples which may be taken out of the mixture prove the fact that stearic acid will be present after a short time in the reaction mass, the quantity of said stearic acid increasing constantly as the process is continued. The samples should be shaken through with ether after having become acid. After 3 hours the iodine number decreased to 40 and the acid number increased to 121; after 6 hours the iodine number was 15 and the acid number 165. The same result is attained if a catalyst containing palladium-chloride is employed. 1

2. 100 parts of cotton oil, previously purified in the ordinary manner, and 100' parts of water are caused to interact with 2 parts of zinc oxide and 10 parts of a nickel carbon catalyst (Ni-contents 20%). Thereupon the apparatus is placed under hydrogen at a pressure of 10 atmospheres and heated to a temperature of 1 about 200. As early as after a few hours the splitting assumes a percentage of approximately 90% of free fatty acids the iodine number of which is half as large as that of the original oil.

3. 100 parts of earth-nut oil and 50 parts of water are caused to interact with 5 parts of a nickel infusorial silica catalyst (Nicontents 20%) and warmed while being well caused to interact in a hydrogen atmosphere to a temperature of 180-200. After three hours a product will be obtained which contains 75% of free acids and having its melting point at 50.

4. 100 parts of linseed oil (iodine number 178) together with 50 parts of water are heated with theaddition of 10 parts of a nickel infusorial silica catalyst (Nicontents 20%) in a stream of hydrogen to a temperature of about 200. After five hours there will have been produced 90% of free acids having an iodine number 64.

5. 100 parts of maize oil (iodine number 113 together with 100 parts of water and 10% ofa nickel infusorial silica catalyst (NP-contents 10%) are heated in a hydrogen atmosphere for two hours to a temperature of 200. The product of reaction has the acid number 165 in accordance with a content of 87% of free acid and the iodine number 17.

6.;The fact that with smaller quantities of a catalyst and some longer time of heating the conditions according to Example 5 may be varied to obtain stronger splitting and smaller hydrogenation is proven by the following composition.

Maize oil (iodine number 110.7) with the addition-of 0.15% of nickel, related to the quantity of fat, in theform of a 10% catalyst, and 150% of water having a temperature of from 200-210 and a pressure of from 2530 atmospheres.

Percent of free acids Iodine number Consistency or Liquid Liquid Gloomy Semi-liquid v Greasy 3537 3840 v glycerine, by means of water, and simultaneously hydrogenating the product by means of a nickelcontaining catalyst and freehydrogen.

3., The process of treating esters of lower monovalent alcohols which consists in decomposing said substances, by means solely of water,

and simultaneously catalytically hydrogenating the products.

4. The process of treating esters of fatty acids which consists in hydrolyzing said esters, by means of water, and simultaneously catalytically hydrogenating the products, said procedure being cone tinu'ediuntil'the fatty acids are completely converted into saturated products.

5., The process of treating fatty acids which consists in dissociating said acids by hydrolysis, solely by means of water, and simultaneously catalytically hydrogenating the resulting products, said hydrolysis and hydrogenation procedures being continued until a mixture of saturated and unsaturated acids is obtained.

6. The process of making fatty acids by dissociation of fats and oils which consists in decomposing fats and oils into free fatty acids and glycerine, by means of water, and simultaneously hydrogenating the product by supplying free hydrogen thereto in the presence of a suitable hydrogenation catalyst.

HANS KAUFMANN. 

